CN107001512B

CN107001512B - Polymer, composition, optical film and liquid crystal display device

Info

Publication number: CN107001512B
Application number: CN201580067490.XA
Authority: CN
Inventors: 田村显夫; 饭岛晃治
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2014-12-12
Filing date: 2015-12-09
Publication date: 2020-03-03
Anticipated expiration: 2035-12-09
Also published as: CN107001512A; KR101973877B1; KR20170083128A; US20170283701A1; JPWO2016092844A1; JP6423002B2; WO2016092844A1

Abstract

The invention provides a polymer which has good wettability and can prevent generation of pits when being added into a composition for coating and film forming, a composition containing the polymer, an optical film which is formed by using the composition and has good surface morphology and no orientation defect, and a liquid crystal display device with the optical film. The invention provides a polymer obtained by polymerizing a monomer having 2 or more free radical polymerizable double bonds and 1 or more hydroxyl groups, a composition containing the polymer, an optical film formed by using the polymer, and a liquid crystal display device provided with the optical film.

Description

Polymer, composition, optical film and liquid crystal display device

Technical Field

The invention relates to a polymer, a composition, an optical film and a liquid crystal display device.

Background

In recent years, polymer materials have been used in various fields. Meanwhile, depending on the field, the properties of the surface of a coating film formed by adding the polymer or the interface of a laminated film when the coating film is laminated are also important, along with the properties of the polymer as a matrix. For example, semiconductor components, optical components, liquid crystal-related components, and the like are often produced by laminating coating films. In order to improve the wettability of the coating composition and the smoothness of the surface of the coating film, or to further improve the wettability when the composition of the upper layer is applied to the surface of the coating film, a silicone-based or fluorine-based surfactant may be added to the composition.

As the fluorine-based surfactant, for example, patent document 1 proposes a fluorine-based surfactant containing a polymer (I) obtained by polymerizing an ethylenically unsaturated monomer (a) containing a fluorinated alkyl group as an essential component and a polymer (II) obtained by polymerizing specific amounts of an ethylenically unsaturated monomer (a) containing a fluorinated alkyl group and an ethylenically unsaturated monomer (B) containing a hydrophilic structural unit as essential components. Accordingly, post-processing suitability such as excellent wettability, uniform coatability, recoatability, and developability can be simultaneously achieved.

On the other hand, in recent years, so-called three-dimensional dendritic polymers (also referred to as dendrimers), such as dendrimers and hyperbranched polymers, have properties different from those of ordinary linear polymers, and their applications have been attracting attention. If a system comprising divinyl monomers is to be free-radically polymerized to synthesize a dendrimer, the monomers are caused to crosslink and an insoluble/infusible polymer is formed. Therefore, non-patent document 1 proposes initiator-incorporated radical polymerization for polymerizing monomers in the presence of a radical polymerization initiator at a high concentration. The polymers produced by this process are highly branched, whereby the melt and solution viscosities are low and the solubility is high.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open No. 2000-102727

Non-patent document

Non-patent document 1: TuneyukiSato, Univ.of Tokushima, p44-52, No.8, Vol.26, No.8, 2006, functional Material

Disclosure of Invention

Technical problem to be solved by the invention

However, the fluorine-based surfactant and the silicone-based surfactant lower the surface tension of the coating film and improve the coating property better in the coating film, but on the other hand, have low surface energy and therefore tend to be biased toward the coating film surface. Since the water and oil repellency of such a surface is increased, when a laminated film is produced by further coating a top layer to form a film, so-called dishing occurs in which the coating liquid is not spread on the coating surface. As a method for preventing the dishing, a method of suppressing fluidity by increasing the viscosity of the coating liquid is conceivable. However, generally, when the viscosity is high, it is difficult to form a uniform coating film.

Fluorine-based surfactants are also used for coating films of optical films of liquid crystal display devices (LCDs) and the like. Some optical films are produced by coating a material containing a liquid crystal compound containing a fluorine-based surfactant on a base film or an alignment film, but the fluorine-based surfactant has poor compatibility with the liquid crystal compound, and the polymer aggregates, resulting in an increase in haze. Further, when a fluorine-based surfactant is also added to the alignment film, dishing is likely to occur. If the orientation film is depressed, the orientation regulating force of the orientation film is hard to act on the interface not in contact with the orientation film, and an orientation defect occurs.

Surfactants other than fluorine-based surfactants and resin modifiers are also poor in solubility and are difficult to use as additives, and development of a novel material capable of improving wettability during coating is required.

In view of the above circumstances, an object of the present invention is to provide a polymer which is less likely to cause dishing by improving wettability of a coating liquid when used as a surfactant, a resin modifier, or the like added to the coating liquid. Also, an object is to provide a composition containing such a polymer and having excellent recoatability.

Another object of the present invention is to provide an optical film that can function as a support film or the like for producing a laminated film, is less likely to cause a sink of a coating liquid for forming an upper layer, has a good surface morphology, and has a surface with reduced alignment defects, and a liquid crystal display device including the optical film.

Means for solving the technical problem

The present inventors have intensively studied to solve the above problems, and as a result, they have found that a polymer obtained by polymerizing a hydroxyl group-containing monomer which is a 2-functional or polyfunctional compound is excellent in compatibility with a base resin and various additives and can suppress aggregation and haze at the time of addition. When the polymer is added to a composition for an optical functional film having a laminated structure and the composition is laminated and coated on a base film and an optical functional layer, no sink is generated at the time of coating a lower layer and at the time of coating an upper layer, and good coatability is exhibited. Further, they found that the obtained film had no orientation defect on the surface and that the surface morphology of the film surface was good, thereby completing the present invention.

That is, the polymer of the present invention is a polymer obtained by polymerizing a monomer having 2 or more radical polymerizable double bonds and 1 or more hydroxyl groups.

The monomer is preferably represented by the following general formula X.

[ chemical formula 1]

In the general formula X, Z^X1、Z^X2Each independently represents a group having a radically polymerizable double bond, L^X1、L^X4Each independently represents a single bond or an alkylene group having a hydroxyl group, L^X2、L^X3Each independently represents a single bond or a 2-valent linking group composed of at least one selected from the group consisting of-O-, - (C ═ O) O-, -O (C ═ O) -, a 2-valent chain group, an alkylene group having a hydroxyl group, and a 2-valent aliphatic cyclic group, M represents a single bond or a 2-to 4-valent linking group, and n represents an integer of 1 to 3.

The monomer is preferably represented by the following general formula X1.

[ chemical formula 2]

In the formula X1, R¹、R²、R³Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, L¹¹、L¹²、L¹³Each independently represents a single bond or a 2-valent linking group composed of at least one selected from the group consisting of-O-, - (C ═ O) O-, -O (C ═ O) -, a 2-valent chain group, an alkylene group having a hydroxyl group, and a 2-valent aliphatic cyclic group, and n1 represents an integer of 0 to 2.

The polymer of the present invention preferably has a partial structure obtained by polymerizing a compound having a fluorine atom.

The compound having a fluorine atom is preferably a compound represented by the following general formula a.

[ chemical formula 3]

In the general formula a, R^a1R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms^a2Represents an alkyl group having 1 to 20 carbon atoms, wherein at least one carbon atom has a fluorine atom as a substituent.

The weight average molecular weight of the polymer of the present invention is preferably 1,000 to 300,000 in terms of polystyrene conversion by gel permeation chromatography.

The weight average molecular weight of the polymer of the present invention is preferably 1,000 to 10,000 in terms of polystyrene conversion by gel permeation chromatography.

The polymers of the invention preferably have a highly branched structure.

The composition of the invention comprises the polymer of the invention.

The composition of the present invention may also be a composition further comprising a liquid crystal compound.

The liquid crystal compound is preferably a polymerizable liquid crystal compound.

The polymerizable liquid crystal compound is preferably at least one of a polymerizable rod-like liquid crystal compound and a polymerizable discotic liquid crystal compound.

The optical film of the present invention is an optical film including a cholesteric liquid crystal layer containing the polymer of the present invention.

The optical film of the present invention may have a structure in which a plurality of cholesteric liquid crystal layers are stacked.

Here, the cholesteric liquid crystal layer refers to a layer in which a composition containing a liquid crystal compound is applied and dried, and then the composition is cured to fix the phase of the liquid crystal compound in cholesteric alignment.

In addition, one of the cholesteric liquid crystal layers may be a cholesteric liquid crystal layer containing a rod-like liquid crystal compound, and the other cholesteric liquid crystal layer may be a cholesteric liquid crystal layer containing a discotic liquid crystal compound.

Preferably, the cholesteric liquid crystal layer including the rod-shaped liquid crystal compound and the cholesteric liquid crystal layer including the discotic liquid crystal compound are in contact with each other.

The liquid crystal display device of the present invention includes at least a backlight unit and a liquid crystal unit provided with the optical film of the present invention.

Effects of the invention

The polymer of the present invention is a polymer obtained by polymerizing a monomer having 2 or more radically polymerizable double bonds and 1 or more hydroxyl groups. With such a structure, when the polymer of the present invention is added to a coating liquid and used, the compatibility with other materials is good, and even the polymer has a hydroxyl group and is polar, so that the affinity with the surface to be coated is high, the wettability is improved, and dishing is less likely to occur. Further, since hydroxyl groups are present on the surface of the coating film, the coating film is less likely to be dented when the upper layer is laminated and coated. Namely, the recoatability was excellent.

Also, an optical film comprising such a polymer has a surface with good surface morphology and reduced orientation defects.

Drawings

Fig. 1 is a schematic cross-sectional view of an optical film according to an embodiment of the present invention.

Fig. 2 is a schematic diagram showing a configuration of a liquid crystal display device according to an embodiment of the present invention.

Fig. 3 is a schematic cross-sectional view of a backlight in a liquid crystal display device according to an embodiment of the present invention.

Detailed Description

The following description is sometimes made based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, a numerical range represented by "to" means a range in which numerical values recited before and after "to" are included as a lower limit value and an upper limit value. In the present specification, the term (meth) acrylate refers to either or both of acrylate and methacrylate.

[ Polymer ]

The polymer of the present invention is a polymer obtained by polymerizing a monomer having 2 or more radically polymerizable double bonds and 1 or more hydroxyl groups.

Such a monomer is preferably a monomer represented by the following general formula X.

[ chemical formula 4]

Z^X1、Z^X2Each independently represents a group having a radical polymerizable double bond. Examples of the group having a self-polymerizable double bond are shown below.

Examples of the group having a radical polymerizable double bond include the following formulas Z1 to Z6.

[ chemical formula 5]

In the formulae Z1 to Z6, R^mRepresents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, and most preferably a hydrogen atom or a methyl group.

Among the above-mentioned formulae Z1 to Z6, the formula Z1 or Z2 is preferable, and the formula Z1 is more preferable.

The polymer of the present invention has a structure in which a large number of branches are present in the molecule, and therefore, the polymer is less entangled among molecular chains, and has high solubility in various solvents and high compatibility with a matrix resin. Therefore, by using the composition containing the polymer of the present invention, a coating film having excellent surface properties can be formed.

L^x1And L^x4Each independently represents a single bond or an alkylene group having a hydroxyl group. L is^x1And L^x4Are each independently preferably-CH₂CH(OH)CH₂-、-CH₂CH(CH₂OH) -, most preferably-CH₂CH(OH) CH₂-。L^x1And L^x4May be the same or different.

L^X2And L^X3Each independently represents a single bond, -O-, - (C ═ O) O-, -O (C ═ O) -, a 2-valent chain group, an alkylene group having a hydroxyl group, a 2-valent aliphatic cyclic group, or a combination thereof. The chain group having a valence of 2 may be a straight chain or a branched chain. As the alkylene group having a hydroxyl group, preferred is-CH₂CH (OH)CH₂-、-CH₂CH(CH₂OH) -, more preferably-CH₂CH(OH)CH₂-。

For L^X2And L^X3Each of which is shown below as an example of a preferred combination.

L is shown below^X2Preferred combinations of (a) and (b). Left side bonded to Z^x1Side, right side bonded to M.

Lx 21: chain group of-O-2 valence

Lx 22: an aliphatic cyclic group having a valence of-O-2-a chain group having a valence of 2-

Lx 23: -OC (═ O) -2 valent aliphatic cyclic group-

Lx 24: -2-valent aliphatic cyclic radical- (C ═ O) O-

Lx 25: - (O-2 valent chain base)_n-

Lx 26: alkylene having an-O-hydroxyl group

L is shown below^X3Preferred combinations of (a) and (b). Left side bonded to M and right side bonded to Z^x2And (3) side.

Lx 31: -2-valent chain radical-O-

Lx 32: a chain group of valence-2 to an aliphatic cyclic group of valence-2-O-

Lx 33: -2-valent aliphatic cyclic radical-C (═ O) O-

Lx 34: -O (C ═ O) -2 valent aliphatic cyclic group-

Lx 35: - (2-valent chain group-O-)_n-

Lx 36: alkylene having a hydroxyl group-O-

The chain group having a valence of 2 is an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group. Preferred are alkylene groups, substituted alkylene groups, alkenylene groups, and substituted alkenylene groups, and more preferred are alkylene groups and alkenylene groups.

The alkylene group may have a branch. The number of carbon atoms of the alkylene group is preferably 1 to 12, more preferably 2 to 10, and most preferably 2 to 8.

The alkylene portion of the substituted alkylene group is the same as the alkylene group described above. Examples of the substituent include a halogen atom.

The alkenylene group may have a branch. The number of carbon atoms of the alkenylene group is preferably 2 to 12, more preferably 2 to 10, and most preferably 2 to 8.

The alkenylene moiety of the substituted alkenylene group is the same as the alkenylene group described above. Examples of the substituent include a halogen atom.

The alkynylene group may have a branch. The carbon number of the alkynylene group is preferably 2 to 12, more preferably 2 to 10, and most preferably 2 to 8.

The alkynylene moiety of the substituted alkynylene group is the same as the alkynylene group described above. Examples of the substituent include a halogen atom.

Specific examples of the 2-valent chain group include: vinyl, trimethylene, propenyl, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene, 2-butynylene, and the like.

The 2-valent aliphatic cyclic group in the general formula X is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.

The ring included in the 2-valent alicyclic group may be either an aliphatic ring or a saturated heterocyclic ring. Examples of the aliphatic ring include a cyclohexane ring, a cyclopentane ring and a norbornene ring.

The aliphatic cyclic group having a valence of 2 may have a substituent. Examples of the substituent include: halogen atom, cyano group, nitro group, alkyl group having 1 to 5 carbon atoms, halogen-substituted alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, alkylthio group having 1 to 5 carbon atoms, acyloxy group having 2 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, carbamoyl group, alkyl-substituted carbamoyl group having 2 to 6 carbon atoms and acylamino group having 2 to 6 carbon atoms. Among them, preferred are alkyl groups having 1 to 5 carbon atoms and halogen-substituted alkyl groups having 1 to 5 carbon atoms.

In the general formula X, n represents an integer of 1 to 3. When n is 2 or 3, there are plural L^X3And L^X4Z may be the same or different and may be present in plural^x2May be the same or different. n is preferably 1 or 2, and more preferably 1.

In the general formula X, M is a single bond or a connecting group with a valence of 2-4. In the general formula X, when n is 1, the linking group has a valence of 2, when n is 2, the linking group has a valence of 3, and when n is 3, the linking group has a valence of 4.

M is preferably a chain group having 2 to 4 valences, a group having an aliphatic cyclic group, or a group having an aromatic ring. The chain-like group having a valence of 2 to 4 represents a saturated hydrocarbon group having 2 to 4 connecting bonds. The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 40, more preferably 1 to 20, and still more preferably 1 to 10. The saturated hydrocarbon group may be straight-chain or branched.

Examples of the group having an aliphatic cyclic group include a cyclohexane ring, a cyclopentane ring, and a norbornene ring.

Examples of the group having an aromatic cyclic group include a phenyl group and a naphthyl group.

The monomer represented by the general formula X is more preferably a monomer represented by the following general formula X1.

[ chemical formula 6]

In the formula X1, R¹、R²、R³Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, L¹¹、L^12、L¹³Each independently represents a single bond or a 2-valent linking group composed of at least one member selected from the group consisting of-O-, - (C ═ O) O-, -O (C ═ O) -, a 2-valent chain group, an alkylene group having a hydroxyl group, and a 2-valent aliphatic cyclic group, and M¹Represents a single bond or a 2-or 3-valent linking group, and n1 represents an integer of 0 to 2.

R¹、R²、R³Preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a hydrogen atom or a methyl group.

L¹¹、L¹²、L¹³And L in the general formula X^x2And L^x3The meaning is the same, and the preferred combinations are the same.

When M is a 2-valent linking group, a monomer represented by the following general formula X2 is preferable.

[ chemical formula 7]

R¹、R²Preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

L¹¹、L¹²Preferably, -O-CH₂-**、*-OCH(CH₃)-**、*-O-C₂H₄-**、 *-O-C₃H₆-**、*-OCH₂CH(OH)CH₂-O-CH is more preferable₂- **. Bonded to a metal in the general formula X2Alkyl side having hydroxy groups, bonded to M¹。

M¹Preferably a single bond, -C₆H₁₀-、-O(C＝O)C₆H₄(C＝O)O-、-O(C＝O)C₆H₁₀(C＝O)O-、-O-C₆H₄-C(CH₃)(CH₃)-C₆H₄-O-。

The polymer of the present invention may have a partial structure obtained by polymerizing a compound having a fluorine atom. The partial structure obtained by polymerizing the compound having a fluorine atom is preferably a structure obtained by radical polymerization of the compound having a fluorine atom represented by the general formula a.

[ chemical formula 8]

In the general formula a, R^a1R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms^a2Represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, wherein at least one carbon atom has a fluorine atom as a substituent.

In the general formula a, R is R from the viewpoint of reducing the surface energy of the composition of the present invention and improving the effect of the present invention^a2Preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which at least one carbon atom has a fluorine atom as a substituent, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably R^a2Half or more of the carbon atoms contained have a fluorine atom as a substituent.

The partial structure obtained by polymerizing the compound having a fluorine atom is more preferably a structure obtained by polymerizing the compound represented by the general formula b.

[ chemical formula 9]

In the general formula b, R^a1Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na represent an integer of 0 or more, and X represents a hydrogen atom or a fluorine atom. ma youAn integer of 1 to 10 is selected, and na is preferably 4 to 12.

Examples thereof include: 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3,3, 3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2, 1H,1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, poly (ethylene glycol) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate, and the like.

The polymer of the present invention may be a polymer obtained by copolymerizing a compound having the above-mentioned fluorine atom. The proportion of the compound having a fluorine atom copolymerized in the polymer of the present invention is preferably 0.01 to 100 mol, more preferably 0.1 to 50 mol, and most preferably 0.5 to 30 mol, based on 1 mol of the monomer preferably having 2 or more radical polymerizable double bonds and 1 or more hydroxyl groups, from the viewpoints of reactivity and surface modification effect.

The polymer of the present invention may have a partial structure derived from a compound having a siloxane bond. The structure derived from the compound having a siloxane bond has a structure represented by the formula-Si (R)^a3)(R^a4) The repeating unit represented by O-may be one, and may constitute at least a part of the molecule. The polymer of the present invention is preferably a graft copolymer in which a polysiloxane structure is introduced into a side chain of the polymer. With respect to the compound having a siloxane bond, in the above general formula a, R^a2Preferably contains-Si (R)^a3)(R^a4) O-, more preferably a structure obtained by polymerizing a compound represented by the following general formula c.

[ chemical formula 10]

R^a3And R^a4Respectively represent an alkyl group, a haloalkyl group or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. Examples thereof include methyl, ethyl and hexyl. The haloalkyl group is preferably a fluoroalkyl group having 1 to 10 carbon atoms. Examples thereof include a trifluoromethyl group and a pentafluoroethyl group. The aryl group preferably has 6 to 20 carbon atoms. Examples thereof include phenyl and naphthyl. Wherein R is^a3And R^a4Preferably methyl, trifluoromethyl or phenyl, particularly preferably methyl.

R^a1And R in the general formula a^a1The meanings are the same, and the preferred ranges are also the same. R^a5Preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

Preferably, nn is 10 to 1000, more preferably 20 to 500, and still more preferably 30 to 200. The above-mentioned repeating unit may be constituted alone or in plural.

The compounds having a siloxane bond for graft copolymerization can be exemplified by: polysiloxane macromonomers having a single-terminal (meth) acryloyl group (e.g., SILAPLANE0721, SILAPLANE0725 (see above, trade name, manufactured by Chisso corporation), AK-5, AK-30, AK-32 (see above, trade name, TOAGOSEI CO., manufactured by LTD.), KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161 AS (see above, trade name, Shin-Etsu Chemical Co., manufactured by Ltd.), etc.).

In the polymer of the present invention, the proportion of the compound having a siloxane bond copolymerized is preferably 0.1 to 50 mol, and particularly preferably 0.1 to 30 mol, based on 1 mol of the monomer having 2 or more polymerizable groups and 1 or more hydroxyl groups, from the viewpoints of reactivity and surface modification effect.

The polymerization initiator is preferably 1 to 15 molar equivalents, more preferably 1 to 10 molar equivalents, and most preferably 2.0 to 10 molar equivalents, relative to 1 mole of the monomer having 2 or more radically polymerizable double bonds and 1 or more hydroxyl groups.

Examples of the compounds represented by the general formula X are shown below. The present invention is not limited to these.

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ composition ]

The composition of the invention comprises the polymer of the invention. The composition of the present invention may further comprise a liquid crystal compound. The liquid crystal compound may be a polymerizable liquid crystal compound. The polymerizable liquid crystal compound is preferably at least one of a polymerizable rod-like liquid crystal compound and a polymerizable discotic liquid crystal compound.

The composition of the present invention can be used for coating and forming an optically anisotropic layer, a liquid crystal layer, a retardation plate, an optical film, an optical compensation film, or the like containing a liquid crystal compound.

Here, the liquid crystal layer includes a layer containing a liquid crystal compound and a polymerizable compound, a layer formed by curing a composition containing a liquid crystal compound and a polymerizable compound, a layer containing a polymerizable liquid crystal compound, or a layer formed by curing a polymerizable liquid crystal compound, and may be hereinafter referred to as a "liquid crystal layer".

(solvent)

The composition of the present invention preferably comprises a solvent. The solvent may be a low surface tension solvent or a standard surface tension solvent. The composition for forming the liquid crystal layer preferably contains a low surface tension solvent.

The surface tension of the low surface tension solvent is 10 to 22mN/m (10 to 22dyn/cm), preferably 15 to 21mN/m, and more preferably 18 to 20 mN/m. The surface tension of the standard surface tension solvent is more than 22mN/m, preferably 23 to 50mN/m, and more preferably 23 to 40 mN/m.

The difference between the surface tension of the low surface tension solvent and the surface tension of the standard surface tension solvent is preferably 2mN/m or more, more preferably 3mN/m or more, further preferably 4 to 20mN/m, and particularly preferably 5 to 15 mN/m.

In the present specification, the surface tension of the solvent is a value described in a solvent handbook (published by Kodansha Company, Limited, 1976). The surface tension of the solvent is a physical property value which can be measured by, for example, an automatic surface tensiometer CBVP-a3 manufactured by Kyowa Interface science co. The measurement can be carried out at 25 ℃.

As the solvent, an organic solvent is preferably used, and among them, a low surface tension solvent and a standard surface tension solvent can be selected. Examples of the organic solvent include: alcohols (e.g. ethanol, t-butanol), amides (e.g. N, N-dimethylformamide), sulfoxides (e.g. dimethyl sulfoxide), heterocycles (e.g. pyridine), hydrocarbons (e.g. heptane, cyclopentane, benzene, hexane, tetrafluoroethylene), haloalkanes (e.g. chloroform, dichloromethane), esters (e.g. methyl acetate, butyl acetate, isopropyl acetate), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone), ethers (e.g. tetrahydrofuran, 1, 2-dimethoxyethane), amines (e.g. triethylamine). Two or more organic solvents may be used in combination.

Examples of the low surface tension solvent include t-butanol (19.5mN/m), tetrafluoroethylene (TFE, 20.6mN/m), triethylamine (20.7mN/m), cyclopentane (21.8mN/m), heptane (19.6mN/m), and mixed solvents including a combination of two or more of these solvents. The values represent surface tension. Among these, from the viewpoint of safety, t-butanol, tetrafluoroethylene, triethylamine and cyclopentane are preferable, t-butanol or tetrafluoroethylene is more preferable, and t-butanol is even more preferable.

Examples of the standard surface tension solvent include methyl ethyl ketone (MEK, 23.9mN/m), methyl acetate (24.8mN/m), methyl isobutyl ketone (MIBK, 25.4mN/m), cyclohexanone (34.5mN/m), acetone (23.7mN/m), isopropyl acetate (22.1mN/m), and a mixed solvent including a combination of any two or more of these solvents. The values represent surface tension. Among them, methyl ethyl ketone, a mixed solvent of cyclohexanone and another solvent, a mixed solvent of methyl acetate and methyl isobutyl ketone, and the like are preferable.

< composition for producing liquid crystal layer >

The polymers of the invention can be used in compositions for the production of liquid-crystalline layers. The composition for producing a liquid crystal layer is a composition comprising the polymer of the present invention and a liquid crystal compound, preferably a polymerizable liquid crystal compound.

The polymer of the present invention provides a composition for producing a liquid crystal layer, which is less likely to cause dishing during coating. Further, it is possible to provide a composition for producing a liquid crystal layer, which is less likely to cause a sink when a coating liquid for forming an upper layer is applied to the surface of a liquid crystal layer formed from the composition for producing a liquid crystal layer as a lower layer and the upper layer is formed. When the composition for producing a liquid crystal layer of the present invention is used, an optical film having a liquid crystal layer in which a depression is not easily generated when a coating liquid for forming is applied can be produced. Therefore, a laminated film having various functions can be produced using the composition for producing a liquid crystal layer of the present invention. Examples of such a laminated film include an optically anisotropic layer, a retardation plate, an optical film, and an optical compensation film.

The composition for producing a liquid crystal layer using the polymer of the present invention contains a hydroxyl group. The hydroxyl group contained in the composition for producing a liquid crystal layer is preferably 0.0001 to 10% by mass based on the liquid crystalline compound.

The present inventors have found that a liquid crystal layer in which a composition containing hydroxyl groups at a constant ratio as described above is less likely to cause dishing when applied and which has a uniform film surface and no unevenness can be produced. In particular, it was found that the dishing in the formation of the upper layer, which is a problem in the production of the laminated film, can be suppressed. The mechanism is not clear, but is presumed as follows. That is, since the polarity of the liquid crystal layer is close to that of the substrate, particularly, the liquid crystal layer thereunder, and the liquid crystal layer is easily wetted and spread at the time of coating, dishing can be prevented.

When the polymer of the present invention is used as a copolymer with a fluorine-containing monomer, the surface migration property is improved, the surface tension of the coating liquid is reduced, and the function of smoothing the surface morphology (leveling) is exhibited. Further, it is considered that the wind resistance to the surrounding environment is improved, optical unevenness is less likely to occur, and dishing can be suppressed.

The composition for producing a liquid crystal layer containing the polymer of the present invention may contain the above-mentioned solvent. The concentration of the solvent is preferably 95 to 50% by mass, more preferably 93 to 60% by mass, and still more preferably 90 to 75% by mass, based on the total mass of the composition for producing a liquid crystal layer.

In the drying step in forming the liquid crystal layer, the solvent of the composition for producing a liquid crystal layer is preferably removed by 95% by mass or more, more preferably removed by 98% by mass or more, still more preferably removed by 99% by mass or more, and in fact, particularly preferably removed by 100% by mass, based on the total amount of the solvent.

(liquid Crystal Compound)

Examples of the liquid crystal compound include rod-like liquid crystal compounds and discotic liquid crystal compounds. The liquid crystal compound includes a low molecular liquid crystal compound. In the present invention, the low molecular weight means a low molecular weight having a degree of polymerization of less than 100. The liquid crystal compound includes a rod-like liquid crystal compound and a discotic liquid crystal compound.

(polymerizable liquid Crystal Compound)

The polymerizable liquid crystal compound means a liquid crystal compound having a polymerizable group. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, an epoxy group, and a vinyl group. Curing the polymerizable liquid crystal compound can fix the alignment of the liquid crystal compound, and can be used as an optical compensation film or the like.

As the rod-like liquid crystal compound, methyleneamines, azoxides, cyanobiphenyls, cyanobenzenes, benzoates, cyclohexanecarboxylic acid benzoates, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolans and alkenylcyclohexylbenzonitrile are preferably used.

As the rod-like liquid crystal compound which is a polymerizable liquid crystal compound, compounds described in Makromol. chem., Vol.190, p.2255 (1989), Vol.5 advanced materials, p.107 (1993), U.S. patent No. 4683327, U.S. Pat. No. 5622648, U.S. Pat. No. 5770107, WO95/22586, WO95/24455, WO97/00600, WO98/23580, WO98/52905, Japanese patent application laid-open No. 1-272551, Japanese patent application laid-open No. 6-16616, Japanese patent application laid-open No. 7-166 110469, Japanese patent application laid-open No. 11-80081, Japanese patent application laid-open No. 2001 64627, and the like can be used. Further, as the rod-like liquid crystal compound, for example, the rod-like liquid crystal compounds described in Japanese patent application laid-open No. 11-513019 or Japanese patent application laid-open No. 2007-279688 can be preferably used.

Examples of discotic liquid crystal compounds include those described in japanese patent application laid-open nos. 2007-108732 and 2010-244038.

(polymerization initiator)

In the case where the composition is cured to form a liquid crystal layer by polymerizing the polymerizable compound, the liquid crystal component may contain a polymerization initiator.

Examples of the polymerization initiator include α -carbonyl compounds (described in U.S. Pat. Nos. 2367661 and 2367670), acyloin ethers (described in U.S. Pat. No. 2448828), α -hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Pat. No. 2722512), polynuclear quinone compounds (described in U.S. Pat. Nos. 3046127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketones (described in U.S. Pat. No. 3549367), acridine and phenazine compounds (described in Japanese patent laid-open publication No. 60-105667 and U.S. Pat. No. 4239850), oxadiazole compounds (described in U.S. Pat. No. 4212970), acylphosphine oxide compounds (described in Japanese patent publication No. 63-40799, Japanese patent publication No. 5-29234, Japanese patent publication No. 10-95788, Japanese patent publication No. 10-29997), and the like.

(chiral reagent)

The liquid crystal layer formed from the composition for liquid crystal layer may be a layer in which a cholesteric liquid crystal phase is fixed. In this case, the composition preferably comprises a chiral agent.

The chiral reagent may be selected from various known chiral reagents (for example, the chiral reagents described in the handbook of liquid crystal devices, chapter 3, items 4-3, TN, STN, pp.199, edited by the first 42 Committee of Japan society of academic interest, 1989). The chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom may also be used as the chiral agent. Examples of the axial asymmetric compound and the planar asymmetric compound include binaphthyl, spiroalkene, paracyclophane, and derivatives thereof. The chiral agent may also have a polymerizable group. When the chiral agent has a polymerizable group and the rod-like liquid crystal compound used together also has a polymerizable group, a polymer having a repeating unit derived from the rod-like liquid crystal compound and a repeating unit derived from the chiral agent can be formed by a polymerization reaction of the chiral agent having a polymerizable group and the polymerizable rod-like liquid crystal compound. In this embodiment, the polymerizable group of the chiral reagent having a polymerizable group is preferably the same kind of group as the polymerizable group of the polymerizable rod-like liquid crystal compound. Therefore, the polymerizable group of the chiral agent is also preferably an unsaturated polymerizable group, an epoxy group or an aziridine group, more preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group.

Also, the chiral agent may be a liquid crystal compound.

Examples of chiral reagents exhibiting a strong twisting force include those described in Japanese patent application laid-open Nos. 2010-181852, 2003-287623, 2002-80851, 2002-80478 and 2002-302487, and can be preferably used. Furthermore, as the isosorbide compounds described in these patent publications, isomannide compounds having a corresponding structure can be used, and as the isosorbide compounds described in these patent publications, isomannide compounds having a corresponding structure can be used.

(fluorine-based surfactant and Silicone-based surfactant)

The composition of the present invention may comprise a fluorine-based surfactant and a silicone-based surfactant. The content of the fluorine-based surfactant and the silicone-based surfactant in the composition for producing a liquid crystal layer is preferably 5% by mass or less based on the total mass of the composition.

The fluorine-containing surfactant is a fluorine-containing compound, and is a compound that is present on the surface of the liquid crystal layer in the solvent used in the composition for producing a liquid crystal layer. Examples of the fluorine-based surfactant having a hydrophobic moiety include a fluorine-containing compound among compounds described as orientation control agents in paragraphs 0028 to 0034 of Japanese patent application laid-open No. 2011-191582, a fluorine-based surfactant described in Japanese patent application laid-open No. 2841611, and fluorine-based surfactants described in paragraphs 0017 to 0019 of Japanese patent application laid-open No. 2005-272560.

Examples of commercially available fluorine-based surfactants include AGC SEIMI CHEMICAL co, Surflon (registered trademark) manufactured by LTD, and Megafac (registered trademark) manufactured by DIC CORPORATION.

The silicone surfactant is a compound containing silicone, and is a compound that is present on the surface of the solvent used in the composition for producing a liquid crystal layer.

Examples of the silicone surfactant include: low molecular weight compounds containing a silicon atom such as polymethylphenylsiloxane, polyether-modified silicone oil, polyether-modified dimethylpolysiloxane, dimethylsilicone, diphenylsilicone, hydrogen-modified polysiloxane, vinyl-modified polysiloxane, hydroxyl-modified polysiloxane, amino-modified polysiloxane, carboxyl-modified polysiloxane, chlorine-modified polysiloxane, epoxy-modified polysiloxane, methacryloxy-modified polysiloxane, mercapto-modified polysiloxane, fluorine-modified polysiloxane, long-chain alkyl-modified polysiloxane, phenyl-modified polysiloxane, and silicone-modified copolymer.

Commercially available Silicone surfactants include KF-96, X-22-945 (manufactured by Shin-Etsu Chemical Co., Ltd., supra), Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone FS 1265-300 (manufactured by Dow Corning Silicone Co., Ltd.), Toray Silicone BYF-4300, TSF-4440, TSF-4445, TSF-4446, TSF-4452, tdF-4460 (manufactured by TOSA TOSIBA SEMI CO., LTD., BYD., BY), Silicone polymers KP341 (manufactured by Shin-Etsu Chemical BYK 341, Co., Ltd., LtS 341, Co-325, BYK-202, BYK-1K-302, BYK-34, BYY-60, BYY, BY, BY., BYK-375 (BYK Japan KK), Aron GS-30 (TOAGOSEI CO., LTD., LT.

[ optical film ]

An optical film according to an embodiment of the present invention will be described with reference to fig. 1. Fig. 1 is a schematic cross-sectional view of an optical film of the present embodiment. In fig. 1, the reduction ratios of the respective portions are appropriately changed for easy recognition. The optical film 10 includes a λ/4 layer 12, a liquid crystal layer 13 adjacent to each other, and a liquid crystal layer 14 on a support 11, and the liquid crystal layer 13 includes a liquid crystal layer containing a liquid crystal compound and a polymer of the present invention or a liquid crystal layer formed by curing a composition containing a liquid crystal compound and a polymer of the present invention. The optical film may be an optical film including only these liquid crystal layers, may be provided with a liquid crystal layer, or may be an optical film including other layers in addition to the liquid crystal layer. Examples of the other layer include an alignment layer and a surface protective layer. Further, the liquid crystal layer other than the liquid crystal layer may be formed from a composition containing the polymer of the present invention.

The optical film 10 preferably includes a layer in which a cholesteric liquid crystal phase is fixed, and the liquid crystal layer 13 is also preferably a layer in which a cholesteric liquid crystal phase is fixed.

As shown in fig. 1, the optical film 10 preferably has a structure including a liquid crystal layer 13, and the liquid crystal layer 13 is formed by applying a composition containing the polymer of the present invention, a liquid crystal component, and a solvent to the surface of the liquid crystal layer 13 as an upper layer, with the liquid crystal layer being a lower layer (liquid crystal layer 13) close to the support 11. The solvent of the composition in this case can be selected from the organic solvents exemplified above. The liquid crystal layer 13 preferably has a structure in which the same layers are further formed on the surface thereof, and the optical film 10 may be a laminated film of 3 to 10 layers of liquid crystal layers formed in the same manner.

In the optical film 10, it is also preferable that one of the liquid crystal layer 13 and the liquid crystal layer 14 is a layer formed of a composition containing a rod-like liquid crystal compound, and the other is a layer formed of a composition containing a discotic liquid crystal compound. Further, it is also preferable that either one of the liquid crystal layer 13 and the liquid crystal layer 14 is a layer formed by curing a composition containing a polymerizable rod-like liquid crystal compound, and the other is a layer formed by curing a composition containing a polymerizable disk-like liquid crystal compound. More preferably, the liquid crystal layer 13 is a layer containing a discotic liquid crystal compound, and the liquid crystal layer 14 is a layer containing a rod-like liquid crystal compound.

The use of the optical film 10 is not particularly limited. Examples of the optical film include a retardation film, a reflection film, and a light absorption film. More specifically, optical compensation films, polarizing films, brightness enhancement films, heat shielding films, and projection films used in liquid crystal display devices and the like are exemplified.

The optical film produced using the polymer of the present invention may be a support film for producing a laminated film, in addition to the form of the optical film 10 of the above embodiment. The support film includes the lower layer (liquid crystal layer 13) described above. The support film contains the liquid crystal layer 13 as the outermost layer, or preferably contains only a film such as a laminate film which can be easily peeled off on the outer side of the liquid crystal layer 13. The liquid crystal layer 13 in the support film is preferably a liquid crystal layer. The liquid crystal layer 13 in the support film is more preferably a layer formed by curing a composition containing a polymerizable discotic liquid crystal compound. The support film may include layers such as a support, an alignment layer, and other liquid crystal layers in addition to the liquid crystal layer 13.

(support)

As the support 11, glass or a polymer film can be used. Examples of the material of the polymer film used as the support include cellulose acylate films (for example, cellulose triacetate films (refractive index 1.48), cellulose diacetate films, cellulose acetate butyrate films, cellulose acetate propionate films), polyolefins such as polyethylene and polypropylene, polyester resin films such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone films, polyacrylic resin films such as polymethyl methacrylate, polyurethane-based resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyether ketone films, (meth) acrylonitrile films, polyolefins, cycloolefin-based polymer films { for example, trade name "ARTON (registered trademark)", manufactured by JSR CORPORATION, trade name "ZEONEX (registered trademark)", manufactured by Zeon CORPORATION }. Among them, triacetyl cellulose, polyethylene terephthalate, and a polymer having an alicyclic structure are preferable, and triacetyl cellulose is particularly preferable.

The support may be a dummy support that is peeled off after the liquid crystal layer is formed and is not included in the optical film.

The thickness of the support may be about 5 to 1000. mu.m, preferably 10 to 250. mu.m, and more preferably 15 to 90 μm.

(alignment layer)

The optical film may include an alignment layer. The alignment layer is used for forming a layer such as a liquid crystal layer, and is used for aligning molecules of a liquid crystal compound contained in a composition for producing a liquid crystal layer.

The optical film may or may not include an alignment layer.

The alignment layer can be provided by a rubbing treatment of an organic compound (preferably a polymer), oblique evaporation of an inorganic compound such as SiO, or a method of forming a layer having microgrooves. Further, an alignment layer that generates an alignment function by applying an electric field, a magnetic field, or light irradiation is also known.

Depending on the material of the lower layer such as the support and the liquid crystal layer, the lower layer can be directly subjected to alignment treatment (for example, rubbing treatment) without providing an alignment layer, thereby functioning as an alignment layer. An example of such a support as a lower layer is polyethylene terephthalate (PET).

In addition, when the liquid crystal layer is directly laminated, the liquid crystal layer in the lower layer may function as an alignment layer, and the liquid crystal compound used for the upper layer may be aligned. In this case, even if no alignment layer is provided and even if no special alignment treatment (e.g., rubbing treatment) is performed, the liquid crystal compound of the upper layer can be aligned.

The rubbing-treated alignment layer and the light alignment layer used by rubbing the surface will be described below as preferred examples.

Rubbing the alignment layer

Examples of the polymer that can be used for the rubbing treatment of the alignment layer include, for example, a methacrylic ester copolymer, a styrene copolymer, a polyolefin, a polyvinyl alcohol and a modified polyvinyl alcohol, poly (N-methylolacrylamide), a polyester, a polyimide, a vinyl acetate copolymer, carboxymethyl cellulose, and a polycarbonate described in paragraph [0022] of Japanese patent application laid-open No. 8-338913. Silane coupling agents may be used as the polymer. The water-soluble polymer (for example, poly (N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol) is preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are most preferable.

The composition is applied to the rubbed surface of the alignment layer to align the molecules of the liquid crystal compound. Then, if necessary, the aforementioned optically anisotropic layer can be formed by reacting an alignment layer polymer with a polyfunctional monomer contained in the optically anisotropic layer or by crosslinking the alignment layer polymer using a crosslinking agent. The film thickness of the orientation layer is preferably in the range of 0.1 to 10 μm.

Friction treatment- -

The surface of the alignment layer, the support, or other layer coated with the composition for liquid crystal layer production may be subjected to rubbing treatment as necessary. The rubbing treatment can be generally performed by rubbing the surface of a film containing a polymer as a main component with paper or cloth in a certain direction. A general method of rubbing treatment is described in "liquid crystal display" (MARUZEN, 10/30/2000).

As a method for changing the rubbing density, the method described in "liquid Crystal Megaku" (distributed by MARUZEN Co., Ltd.) can be used. The friction density L was quantified by the following formula a.

Formula AL ═ Nl (1+2 pi rn/60v)

In the formula A, N is the number of times of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, N is the rotational speed (rpm) of the roller, and v is the stage moving speed (second speed).

In order to increase the friction density, the number of times of friction is increased, the contact length of the friction roller is increased, the radius of the roller is increased, the rotation speed of the roller is increased, and the moving speed of the platform is reduced. On the other hand, in order to reduce the friction density, the opposite may be performed. Further, as a condition for the rubbing treatment, the description of japanese patent No. 4052558 may be referred to.

Photo-alignment layer

Many documents and the like describe a photo-alignment material used for a photo-alignment layer formed by light irradiation. Preferred examples include: japanese patent laid-open Nos. 2006-285197, 2007-76839, 2007-138138, 2007-94071, 2007-121721, 2007-140465, 2007-156439, 2007-133184, 2009-109831, 3883848, 4151746 azo compounds, 2002-229039 aromatic ester compounds, 2002-265541, 2002-317013 maleimide and/or alkenyl-substituted maleimide (nadiimide) compounds having a photo-alignment unit, 4205195, 4205198 photo-crosslinkable silane derivatives, A photo-crosslinkable polyimide, polyamide or ester described in JP-A-2003-520878, JP-A-2004-529220 and JP-A-4162850. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides or esters.

The light alignment layer formed of the above material is irradiated with linearly polarized light or unpolarized light to produce a light alignment layer.

In the present specification, "linearly polarized light irradiation" is an operation for causing photoreaction of the photo-alignment material. The wavelength of light used differs depending on the photo-alignment material used, and is not particularly limited as long as it is a wavelength necessary for the photoreaction. The peak wavelength of light used in the light irradiation is preferably 200nm to 700nm, and more preferably, the peak wavelength of light is ultraviolet light having a wavelength of 400nm or less.

Examples of the light source used for light irradiation include commonly used light sources such as a tungsten lamp, a halogen lamp, a xenon flash lamp, a mercury xenon lamp, a carbon arc lamp, and the like, various lasers (e.g., a semiconductor laser, a helium-neon laser, an argon ion laser, a helium-cadmium laser, a YAG laser), a light emitting diode, a cathode ray tube, and the like.

As a method of obtaining linearly polarized light, the following method can be employed: a method using a polarizing plate (e.g., iodine polarizing plate, dichroic dye polarizing plate, wire grid polarizing plate); methods using reflective polarizers using prism-like elements (e.g., Glan-Thomson prisms) or Brewster's angle; or a method of using light emitted from a laser light source having polarized light. Further, only light of a desired wavelength may be selectively irradiated using a filter, a wavelength conversion element, or the like.

When the light to be irradiated is linearly polarized light, a method of irradiating light from the upper surface or the back surface in a direction perpendicular or oblique to the surface of the alignment layer may be employed for the alignment layer. The incident angle of light differs depending on the photo-alignment material, and is, for example, 0 ° to 90 °, and preferably 40 ° to 90 °. The 90 ° is now vertical.

When unpolarized light is used, unpolarized light is obliquely irradiated. The incident angle is 10 to 80 degrees, preferably 20 to 60 degrees, and particularly preferably 30 to 50 degrees.

The irradiation time is preferably 1 minute to 60 minutes, and more preferably 1 minute to 10 minutes.

(method for producing optical film)

The optical film can be manufactured by forming a liquid crystal layer on a support. The support may be peeled off after the liquid crystal layer is formed. In the present specification, the term "on the support" means "directly on the support surface" or "through another layer formed on the support surface". The liquid crystal layer may also be formed on the surface of other layers previously formed.

It is also preferable that the liquid crystal layer as described above is further formed on the surface of the liquid crystal layer. The liquid crystal layer formed from the composition for producing a liquid crystal layer of the present invention is less likely to cause a sag, and thus various laminated optical films can be produced. The composition of the invention is particularly preferably applied directly to the surface of a previously formed liquid crystal layer. The composition of the present invention is less likely to cause dishing when applied to form a film, has an excellent surface morphology, and is capable of reducing orientation defects.

(formation of liquid Crystal layer)

The liquid crystal layer is formed from a coating film comprising the composition of the present invention. The liquid crystal layer may be a layer formed by applying the composition to a support and drying the obtained coating film, or may be a layer formed by further performing a curing step such as light irradiation or heating.

The composition of the present invention can be applied by a method of spreading the composition in an appropriate manner such as a roll coating method, a gravure printing method, a spin coating method, or the like. Further, the coating can be carried out by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. Further, the composition can be discharged from a nozzle using an ink jet device to form a coating film.

Drying may be carried out by standing or by heating. In the drying step, an optical function derived from the liquid crystal component can be expressed. For example, when the liquid crystal composition contains a liquid crystal compound, a liquid crystal phase may be formed during the process of removing the solvent by drying. The formation of the liquid crystal phase can be performed at a temperature at which the liquid crystal phase is transformed into the liquid crystal phase by heating. For example, the liquid crystal phase can be stably brought into a state by heating the liquid crystal phase to the temperature of the isotropic phase once and then cooling the liquid crystal phase to the liquid crystal phase transition temperature. The liquid crystal phase transition temperature is preferably within a range of 10 to 250 ℃ and more preferably within a range of 10 to 150 ℃ from the viewpoint of manufacturing suitability and the like. If the temperature is less than 10 ℃, a cooling step or the like may be required to lower the temperature to a temperature range in which a liquid crystal phase is present. Further, if the temperature exceeds 200 ℃, a high temperature is required to temporarily bring the liquid crystal into an isotropic liquid state having a temperature higher than the temperature range in which the liquid crystal phase is present, and this is disadvantageous from the viewpoint of waste of thermal energy, deformation, alteration, and the like of the substrate.

For example, when the composition contains a polymerizable compound, the dried film is preferably cured. When the composition contains a polymerizable liquid crystal compound, the composition can be fixed by curing the composition while maintaining the alignment state of the molecules of the liquid crystal compound. Curing can be performed by a polymerization reaction of a polymerizable group in the polymerizable compound.

The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Photopolymerization is preferred. The light irradiation for polymerization of the polymerizable compound, particularly the liquid crystal compound, is preferably ultraviolet light. The irradiation energy is preferably 50mJ/cm²～1000mJ/cm²More preferably 100 to 800mJ/cm². In order to promote the photopolymerization reaction, the light irradiation may be performed under heating conditions.

In order to accelerate the curing reaction, ultraviolet irradiation may be performed under heating conditions. Further, since the oxygen concentration in the atmosphere is related to the degree of polymerization, when the desired degree of polymerization is not reached in the air and the film strength is insufficient, it is preferable to lower the oxygen concentration in the atmosphere by a method such as nitrogen substitution. The oxygen concentration is preferably 10% by volume or less, more preferably 7% by volume or less, and most preferably 3% by volume or less.

The reaction rate of the curing reaction (for example, polymerization reaction) by ultraviolet irradiation is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more, from the viewpoint of maintaining the mechanical strength of the layer, suppressing the flow of unreacted materials out of the layer, and the like. In order to increase the reaction rate, a method of increasing the irradiation amount of ultraviolet rays to be irradiated and polymerization under a nitrogen atmosphere or under heating are effective. Further, a method of further advancing the reaction by the thermal polymerization reaction by holding the polymer at a temperature higher than the polymerization temperature after the temporary polymerization, and a method of irradiating ultraviolet rays again may be used. The reaction rate can be measured by comparing the absorption intensity of the infrared vibration spectrum of the reactive group (for example, polymerizable group) before and after the reaction.

The optical properties based on the alignment of the liquid crystal compound molecules in the liquid crystal layer using the liquid crystal compound as a liquid crystal component, for example, only the optical properties of a cholesteric liquid crystal phase need to be maintained in the layer, and the liquid crystal composition of the liquid crystal layer after curing does not need to exhibit liquid crystallinity. For example, the liquid crystal compound molecules may be increased in molecular weight by a curing reaction to lose liquid crystallinity in advance.

The liquid crystal layer is preferably a cholesteric liquid crystal layer in which the orientation of the cholesteric liquid crystal phase is fixed. As the cholesteric liquid crystal layer and the method for producing the cholesteric liquid crystal layer, for example, the descriptions of japanese unexamined patent publication No. 1-133003, japanese unexamined patent publication No. 3416302, japanese unexamined patent publication No. 3363565, and japanese unexamined patent publication No. 8-271731 can be cited.

[ liquid Crystal display device ]

The optical film of the present invention can be used as a brightness enhancement film used in a backlight of a liquid crystal display device. Hereinafter, a liquid crystal display device which is one embodiment of the present invention will be described. Fig. 2 is a schematic diagram showing a structure of a liquid crystal display device 20 according to an embodiment of the present invention. Fig. 3 is a schematic sectional view of the backlight unit.

As shown in fig. 2, the liquid crystal display device 20 includes a pair of polarizing plates (an upper polarizing plate 21 and a lower polarizing plate 28), a liquid crystal cell 30 sandwiched therebetween, and a backlight unit 40 disposed on the opposite surface side of the liquid crystal cell of the lower polarizing plate 28, and the liquid crystal cell 30 includes a liquid crystal 25, an upper electrode substrate 23 of the liquid crystal cell disposed above and below the liquid crystal cell, and a lower electrode substrate 26 of the liquid crystal cell. Since the backlight unit 40 includes the polarized light emitting film, the lower polarizing plate 28 can be omitted.

When the liquid crystal display device 20 is used as a transmissive type, the upper polarizing plate 21 is used as a front side (visible side) polarizing plate, and the lower polarizing plate 28 is used as a rear side (backlight side) polarizing plate, and although not shown, a color filter is provided between the liquid crystal 25 and the upper polarizing plate 21. In fig. 2, 22 and 29 indicate directions of absorption axes of the respective polarizing plates which are substantially orthogonal to each other, and 24 and 27 indicate orientation control directions of the respective electrode substrates.

As shown in fig. 3, the backlight unit 40 includes: emitting primary light (blue light L)_B) The light source 42; a light guide plate 43 for guiding the primary light emitted from the light source 42 to emit the primary light; a wavelength conversion member 44 disposed on the light guide plate 43; a luminance enhancement film 45 disposed opposite to the light source 42 with the wavelength conversion member 44 interposed therebetween; and a reflection plate 41 disposed opposite to the wavelength conversion member 44 with a light guide plate 43 interposed therebetween. The wavelength conversion member 44 converts the primary light L emitted from the light source 42_BEmits fluorescence as excitation light, and emits secondary light (L) including the fluorescence_G、L_R) And the primary light L transmitted through the wavelength conversion member 44_B. The backlight unit 40 passes the secondary light (L)_G、L_R) And the primary light L transmitted through the wavelength conversion member 44_BAnd emits white light L_w。

Brightness enhancement film 45 has optical film 10 of the present invention.

As the light source 42, a light source that emits blue light having a light emission center wavelength in a wavelength band of 430nm to 480nm, for example, a blue light emitting diode that emits blue light can be used. When a light source emitting blue light is used, the wavelength conversion member 44 preferably includes at least quantum dots R excited by excitation light to emit red light and quantum dots G emitting green light. Thereby, white light can be realized by blue light emitted from the light source and transmitted through the wavelength conversion member, red light and green light emitted from the wavelength conversion member.

Alternatively, in another aspect, a light source that emits ultraviolet light having an emission center wavelength in a wavelength band of 300nm to 430nm, for example, an ultraviolet light emitting diode, can be used as the light source. At this time, the wavelength conversion member 44 preferably includes quantum dots R, G and quantum dots B that are excited by the excitation light and emit blue light. Thereby, white light can be realized by red light, green light, and blue light emitted from the wavelength conversion member.

In another embodiment, a laser light source can be used instead of the light emitting diode.

The light source may include a light source that emits blue light having an emission center wavelength in a wavelength band of 430 to 500nm, green light having an emission center wavelength in a wavelength band of 500 to 600nm, and red light having at least a part of a peak of emission intensity in a wavelength band of 600 to 700nm, and therefore, a white light source such as a white LED (light emitting diode) may be used as a light source other than the above-described light sources.

When the backlight unit 40 includes the light guide plate 43, the wavelength conversion member 44 is disposed on the path of light emitted from the light guide plate 43. A known light guide plate can be used as the light guide plate 43 without any limitation. The backlight unit 40 may include a reflecting member at the rear of the light source. Such a reflecting member is not particularly limited, and known reflecting members can be used, and are described in japanese patent No. 3416302, japanese patent No. 3363565, japanese patent No. 4091978, japanese patent No. 3448626, and the like, and the contents of these publications are incorporated in the present invention.

The backlight unit 40 preferably further includes other known diffusion plates, diffusion sheets, prism sheets (for example, BEF series manufactured by Sumitomo 3 MLimited), and light guides. Other members are also described in japanese patent No. 3416302, japanese patent No. 3363565, japanese patent No. 4091978, japanese patent No. 3448626, and the like, and the contents of these publications are incorporated in the present invention.

In the liquid crystal display device provided in the backlight unit, the driving mode of the liquid crystal cell is not particularly limited, and various modes such as Twisted Nematic (TN), Super Twisted Nematic (STN), Vertical Alignment (VA), in-plane switching (IPS), and optically compensated bend alignment (OCB) can be used. The liquid crystal cell is preferably a VA mode, an OCB mode, an IPS mode, or a TN mode, but is not limited thereto. As an example of the structure of the VA mode liquid crystal display device, a structure shown in fig. 2 of japanese patent application laid-open No. 2008-262161 is given. However, the specific structure of the liquid crystal display device is not particularly limited, and a known structure can be employed.

By providing the optical film of the present invention to the luminance enhancement film of the backlight unit, the wavelength conversion regions of red and green colors are widened, and a backlight and a liquid crystal display device having high luminance can be obtained.

Examples

The present invention will be described in more detail with reference to examples. The materials, reagents, substances, amounts thereof, ratios thereof, operations and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following examples.

< Synthesis example 1 >

(Synthesis example of Polymer B-101)

25.0g of t-amyl alcohol was placed in a 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet and the temperature was raised to 120 ℃. Subsequently, a mixed solution including 3.25g (7.8 mmol) of 2- (perfluorohexyl) ethylene acrylate, 2.26g (4.7 mmol) of the monomer A shown below, i.e., the 3-functional hydroxyl group-containing compound, 25.0g of t-amyl alcohol, and 6.0g of a polymerization initiator "V-601" (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at a constant rate so that the dropwise addition was completed within 30 minutes. After completion of the dropwise addition, further stirring was continued for 3.5 hours, and then the solvent was distilled off under reduced pressure and dried under reduced pressure at 130 ℃ to obtain 7.7g of polymer B-101 of the present invention. The weight average molecular weight (Mw) of the polymer was 1,800. The weight average molecular weight (Mw) was calculated as polystyrene conversion by Gel Permeation Chromatography (GPC). The columns used were TSKgelSuperHZM-H, TSKgelSuperHZ4000, TSKgelSuperHZ200 (manufactured by Tosoh Corporation).

Table 1 shows the materials and contents of the respective synthesis examples.

[ chemical formula 16]

[ chemical formula 17]

< Synthesis examples 2 to 10 >

Polymers B-102 to B-110 of the present invention were synthesized in the same manner as in Synthesis example 1, except that the monomers and the composition ratio were changed as shown in Table 1. The synthesis examples 2 to 10 had a weight average molecular weight (Mw) of 1,600 to 3,600.

The monomer B, C, D used in Synthesis examples 2 to 10 is shown below.

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

Table 1 shows the materials, contents and molecular weights of Synthesis examples 1 to 10. In the table, the hydroxyl group-containing monomer represents a compound having 2 or more radical polymerizable double bonds and 1 or more hydroxyl groups, and the fluorine-containing monomer represents a compound having the above-mentioned fluorine atom.

In addition, the abbreviations in Table 1 have the following meanings.

C6 FHA: 1H,1H, 7H-dodecafluoroheptyl acrylate

C6 FA: 2- (perfluorohexyl) ethylene acrylate

C8 FA: 2- (Perfluorooctyl) ethylene acrylate

C10 FA: 2- (perfluorodecyl) ethylene acrylate

Production of optical film

Optical films of examples and comparative examples were produced using the polymers of B-101 to B-110 obtained in the above. The optical film is formed by sequentially laminating an alignment layer, a λ/4 layer, an alignment layer, a liquid crystal layer 1 (hereinafter, also referred to as a lower layer), and a liquid crystal layer 2 (hereinafter, also referred to as an upper layer) on a support. The method for forming each layer and the coating liquid will be described below.

< support body: TD40UL >

A commercially available cellulose acylate film "TD 40 UL" (manufactured by Fujifilm Corporation) was used as the support. Hereinafter, the support is referred to as TD40 UL.

< TD40UL + orientation layer >

The surface of TD40UL was subjected to an alkaline treatment to form an alignment layer.

Alkali saponification treatment-

TD40UL was passed through a dielectric heating roller having a temperature of 60 ℃ to raise the surface temperature of the film to 40 ℃ and then one surface of the film was coated with a bar coater at a rate of 14ml/m²The coating amount of (a) was applied with an alkali solution having the following composition, and the coating was transferred for 10 seconds under a NORITAKE CO. heated to 110 ℃ and a steam type far infrared heater made of LIMITED. Next, a bar coater was also used at 3ml/m²Pure water was applied. Subsequently, washing with water using a jet coater (fountain coater) and dehydration using an air knife were repeated 3 times, and then the film was transferred to a drying zone at 70 ℃ for 10 seconds to be dried, thereby producing an alkali-saponified cellulose acylate film.

Composition of the alkali solution

4.7 parts by mass of potassium hydroxide

15.8 parts by mass of water

Isopropyl alcohol 63.7 parts by mass

Surfactant SF-1: c₁₄H₂₉O(CH₂CH₂O)₂₀H1.0 part by mass

14.8 parts by mass of propylene glycol

Formation of an alignment layer

An alignment layer coating liquid having the following composition was continuously applied to the long cellulose acetate film subjected to the alkali saponification treatment as described above by using a wire rod # 14. The mixture was dried with warm air at 60 ℃ for 60 seconds, and further dried with warm air at 100 ℃ for 120 seconds. The obtained coating film was continuously subjected to rubbing treatment to prepare an alignment layer. At this time, the longitudinal direction of the long film is parallel to the transport direction, and the rotation axis of the rubbing roller is set to a direction rotated by 45 ° clockwise with respect to the film longitudinal direction.

Composition of alignment layer coating liquid-

10 parts by mass of modified polyvinyl alcohol

371 parts by mass of water

119 parts by mass of methanol

Glutaraldehyde 0.5 parts by mass

0.3 part by mass of photopolymerization initiator (IRGACURE2959, manufactured by BASF corporation)

The structural formula of the modified polyvinyl alcohol in the alignment layer coating liquid is shown below. In the following structural formula, the ratio is a molar ratio.

[ chemical formula 21]

< TD40UL + orientation layer + lambda/4 layer >

Coating liquid A1 containing a discotic liquid crystalline compound having the following composition was continuously applied to the above-prepared liquid crystal film by means of a #3.6 wire barOn the orientation layer. The film transport speed (V) was set to 20 m/min. The coating liquid was heated with a warm air of 60 ℃ for 90 seconds to dry the solvent of the coating liquid and age the discotic liquid crystal compound. Subsequently, UV irradiation was performed at 60 ℃ to fix the alignment of the liquid crystal compound, thereby forming a lambda/4 layer. In this case, the UV irradiation dose was set to 100mJ/cm²。

Coating liquid A1 used in the layer of-lambda/4-

80 parts by mass of discotic liquid-crystalline compound (Compound 101)

Discotic liquid crystal compound (compound 102)20 parts by mass

Orientation assistant 10.9 parts by mass

Orientation assistant 20.1 parts by mass

10 parts by mass of a polymerizable monomer

0.12 part by mass of a surfactant (MegafacF 444 manufactured by DIC Corporation)

Polymerization initiator 13 parts by mass

192.1 parts by mass of acetone

Tertiary butanol 54.9 weight portions

Cyclohexanone 27.5 parts by mass

[ chemical formula 22]

The orientation assistant 1 and the orientation assistant 2 are each a mixture of 2 compounds having different methyl substitution positions in a trimethyl-substituted benzene ring. The mixing ratio of the 2 compounds is 50: 50.

the following description shows other coating liquids (a2, A3) used for the λ/4 layer and the formation method thereof.

Coating liquid a2 containing a discotic liquid crystalline compound having the following composition was continuously applied onto the alignment layer by a wire bar of # 3.0. The film transport speed (V) was set to 20 m/min. The coating liquid was heated with a warm air of 60 ℃ for 60 seconds to dry the solvent of the coating liquid and age the discotic liquid crystal compound. Subsequently, UV irradiation was performed at 70 ℃ to fix the alignment of the liquid crystal compound, thereby forming a lambda/4 layer. At this time, UThe V dose was set to 200mJ/cm²。

Coating liquid A2 containing discotic liquid-crystalline compound

80 parts by mass of discotic liquid-crystalline compound (Compound 101)

Discotic liquid crystal compound (compound 102)20 parts by mass

Orientation assistant 10.9 parts by mass

Orientation assistant 20.1 parts by mass

10 parts by mass of a polymerizable monomer

0.12 part by mass of a surfactant (MegafacF 444, manufactured by DIC Co., Ltd.)

Polymer B-1010.03 parts by mass of the present invention

Polymerization initiator 13 parts by mass

218.7 parts by mass of methyl ethyl ketone

Tert-butanol 62.5 parts by mass

Cyclohexanone 31.2 parts by mass

Coating liquid a3 containing a discotic liquid crystalline compound having the following composition was continuously applied onto the alignment layer by a wire bar of # 3.0. The film transport speed (V) was set to 20 m/min. The coating liquid was heated with a warm air of 60 ℃ for 60 seconds to dry the solvent of the coating liquid and age the discotic liquid crystal compound. Subsequently, UV irradiation was performed at 70 ℃ to fix the alignment of the liquid crystal compound, thereby forming a lambda/4 layer. In this case, the UV irradiation dose was set to 200mJ/cm²。

Coating liquid A3 containing discotic liquid-crystalline compound

80 parts by mass of discotic liquid-crystalline compound (Compound 101)

Discotic liquid crystal compound (compound 102)20 parts by mass

Orientation assistant 10.9 parts by mass

Orientation assistant 20.1 parts by mass

10 parts by mass of a polymerizable monomer

Polymer B-1010.05 parts by mass of the present invention

Polymerization initiator 13 parts by mass

218.7 parts by mass of methyl ethyl ketone

Tert-butanol 62.5 parts by mass

Cyclohexanone 31.2 parts by mass

< TD40UL + alignment layer + lambda/4 layer + alignment layer >

An alignment layer was formed on the surface of the λ/4 layer in the same manner as described above.

< TD40UL + alignment layer + lambda/4 layer + alignment layer + liquid crystal layer 1 (lower layer) >

The surface of the alignment layer formed on the λ/4 layer was continuously coated with the following coating liquid adjusted to a film thickness of 3 μm. Subsequently, the solvent was dried at 70 ℃ for 2 minutes, evaporated, and then heat-aged at 115 ℃ for 3 minutes to obtain a uniform alignment state. After that, the coated film was kept at 50 ℃ and irradiated with ultraviolet rays using a high-pressure mercury lamp under a nitrogen atmosphere, and a cholesteric liquid crystal layer 1 was formed. In this case, the UV irradiation dose was 75mJ/cm²。

(preparation of coating liquid B1 used in liquid Crystal layer 1 of example 1)

Composition of a liquid crystal layer B1

80 parts by mass of discotic liquid-crystalline compound (Compound 101)

Discotic liquid crystal compound (compound 102)20 parts by mass

Polymer B-1010.05 parts by mass of the present invention

Polymerization initiator 13 parts by mass

15.5 parts by mass of chiral reagent

Methyl ethyl ketone 6.7 parts by mass

112.6 parts by mass of acetone

38.8 parts by mass of tert-butanol

15 parts by mass of cyclohexanone

The chiral agent used in the composition of the liquid crystal layer B1 is shown below.

[ chemical formula 23]

(preparation of coating solutions for use in liquid Crystal layer 1 in examples 2 to 18 and comparative examples 1 to 4)

Coating liquids B2 to B18 according to the present invention and coating liquids BH-1 to BH-4 according to comparative examples were prepared in the same manner as coating liquid B1, except that the amount and type of the polymer to be added according to the present invention were as described in Table 1.

(coating solution and Forming method of liquid Crystal layer 1 in example 19)

The surface of the alignment layer formed on the surface of the λ/4 layer of the TD40UL + λ/4 layer was continuously coated with the following coating liquid B19 adjusted to a film thickness of 3.1 μm. Subsequently, the solvent was dried at 70 ℃ for 1 minute, the solvent was vaporized, and then heat aging was performed at 112 ℃ for 2 minutes, whereby a uniform alignment state was obtained.

Thereafter, the coated film was kept at 50 ℃ and irradiated with ultraviolet rays under a nitrogen atmosphere using a metal halide lamp manufactured by EYE GRAPHICS, whereby a cholesteric liquid crystal layer B19 was formed. The nitrogen atmosphere is an environment having an oxygen concentration of 500ppm or less. In this case, the UV irradiation dose was 130mJ/cm²。

Coating liquid B19 for liquid crystal layer 1 in example 19

80 parts by mass of discotic liquid-crystalline compound (Compound 101)

Discotic liquid crystal compound (compound 102)20 parts by mass

0.18 part by mass of a surfactant (MegafacF 444, manufactured by DIC Co., Ltd.)

Compound B-1010.03 parts by mass of the present invention

Polymerization initiator 13 parts by mass

15.1 parts by mass of chiral reagent

Methyl ethyl ketone 125.2 parts by mass

38.5 parts by mass of tert-butanol

Cyclohexanone 28.9 parts by mass

(coating solution and Forming method of liquid Crystal layer 1 in example 20)

The surface of the alignment layer formed on the surface of the λ/4 layer of the TD40UL + λ/4 layer was continuously coated with the following coating liquid B20 adjusted to a film thickness of 3.1 μm. Subsequently, the solvent was dried at 70 ℃ for 1 minute, the solvent was vaporized, and then heat aging was performed at 112 ℃ for 2 minutes, whereby a uniform alignment state was obtained.

Thereafter, the coated film was kept at 50 ℃ and irradiated with ultraviolet rays under a nitrogen atmosphere using a metal halide lamp manufactured by EYE GRAPHICS, whereby a cholesteric liquid crystal layer B20 was formed. The nitrogen atmosphere is an environment having an oxygen concentration of 500ppm or less. In this case, the UV irradiation dose was 130mJ/cm²。

Coating liquid B20 for liquid Crystal layer 1 in example 20

80 parts by mass of discotic liquid-crystalline compound (Compound 101)

Discotic liquid crystal compound (compound 102)20 parts by mass

Compound B-1010.05 parts by mass of the present invention

Polymerization initiator 13 parts by mass

15.1 parts by mass of chiral reagent

Methyl ethyl ketone 125.2 parts by mass

38.5 parts by mass of tert-butanol

Cyclohexanone 28.9 parts by mass

< TD40UL + lambda/4 layer + alignment layer + liquid crystal layer 1+ liquid crystal layer 2 (upper layer) >

Coating liquid C1 containing a rod-like liquid crystal compound having the following composition was continuously applied to the surface of the liquid crystal layer 1 prepared from coating liquid B1, with the film thickness adjusted to 5 μm. The film transport speed was set to 20 m/min. The coating liquid was heated with a warm air of 95 ℃ for 180 seconds to dry the solvent of the coating liquid and age the alignment of the rod-like liquid crystal compound. Subsequently, UV irradiation was performed at 30 ℃ to fix the alignment of the liquid crystal compound, thereby forming an optically anisotropic layer (liquid crystal layer 2). In this case, the UV irradiation dose was set to 300mJ/cm²。

A liquid crystal layer 2 was formed in the same manner as in examples 1 to 20 and comparative examples 1 to 4.

Coating liquid C1 of the liquid crystal layer 2

20183 parts by mass of rod-like liquid crystalline compound

Rod-like liquid crystal compound 20215 parts by mass

2032 parts by mass of a rod-like liquid crystalline compound

Polyfunctional monomer A-TMMT (SHIN-NAKAMURA CHEMICAL CO., LTD. manufactured)

1 part by mass

Polymerization initiator IRGACURE819 (manufactured by BASF) 4 parts by mass

10.17 parts by mass of a fluorine-containing compound

Chiral reagent LC756(BASF corporation) 6 parts by mass

187.5 parts by mass of toluene

Cyclohexanone 9.9 parts by mass

[ chemical formula 24]

[ chemical formula 25]

(comparative Synthesis example 1)

In a 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 25.0g of toluene was charged and the temperature was raised to 120 ℃. Next, a mixed solution comprising 3.25g (7.8 mmol) of 2- (perfluorohexyl) ethylene acrylate, 2.26g (5.3 mmol) of trimethylolpropane triacrylate, 25.0g of toluene and 4.7g of a polymerization initiator "V-601" (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at a constant rate so that the dropwise addition was completed within 30 minutes. After completion of the dropwise addition and further stirring for 3.5 hours, the solvent was distilled off under reduced pressure and dried under reduced pressure at 130 ℃ to obtain 7.5g of a comparative polymer (H-101). The weight average molecular weight (Mw) of the polymer was 1,500. The weight average molecular weight (Mw) was calculated in terms of polystyrene by Gel Permeation Chromatography (GPC). The columns used were TSKgelSuperHZM-H, TSKgelSuperHZ4000, TSKgelSuperHZ200 (manufactured by Tosoh Corporation).

[ chemical formula 26]

[ chemical formula 27]

(comparative example Compound H-103)

A commercially available fluorine-based surface modifier "MegafacF-552" (trade name, manufactured by DIC) was used.

(measurement of viscosity of coating liquid)

The viscosities of the coating liquids B1 to B20, BH-1 to BH-4, and C1 were measured using a vibration viscometer (trade name "Vm-100", manufactured by SEKONIC CORPORATION). All of them are in the range of 1.5 to 10 mPas.

The following items were evaluated after coating and drying the liquid crystal layer 1 and the liquid crystal layer 2 of the optical film thus produced. The results are shown in Table 2.

< recess >

The number of dents of the layer formed using each composition in 15cm × 20cm of the film of each example and comparative example was counted. Here, the number of regions where the upper layer is not formed in the surface of the lower layer is counted as one depression. Based on the results, evaluation was performed on the following criteria.

When the evaluation criterion is a or B, the production efficiency is excellent and can be preferably used. The evaluation criterion is more preferably A.

A: the number of depressions is 1 or less

B: 2 to 3 depressions

C: the number of the depressions is 4-9

D: more than 10 depressions

< surface morphology >

The surface morphology of the layer after drying the coating composition was visually confirmed.

When the evaluation criterion is a or B, the production efficiency is excellent and can be preferably used, and the evaluation criterion is more preferably a.

A: is in a surface form without drying unevenness or wrinkles

B: drying was slightly uneven, but could be used without any problem

C: uneven drying or more uneven portions than B can be used without any problem

D: the remarkable unevenness caused by uneven drying was found to be unsuitable for use

< orientation >

The quality of the liquid crystal alignment was determined based on the presence or absence of alignment defects when the film was observed with a polarizing microscope (trade name "ECLIPSE", manufactured by Nikon corporation) according to the following criteria. The evaluation criterion is preferably any of the evaluations A to C. The evaluation criterion a or B is excellent in production efficiency and can be preferably used, and the evaluation criterion a is more preferable.

A: no poor orientation

B: almost no orientation defect

C: some of them found to be slightly misoriented

D: the entire surface has poor orientation

< liquid crystal display device >

When a commercially available liquid crystal display device (trade name "TH-L42D 2", manufactured by Panasonic Corporation) was decomposed and the luminance enhancement film located in the backlight unit was changed to the optical film of the present invention, the liquid crystal display device of the present invention exhibited good performance.

As is clear from Table 2, examples 1 to 20 using the polymer of the present invention can obtain good results in all of the depressions, the surface morphology and the orientation. In particular, in examples 1 to 8 in which the polymer contains a radical polymerizable double bond and a partial structure obtained by copolymerizing a compound having a fluorine atom, all of the superiorities in evaluation of the lower layer and the upper layer were evaluated as a in comparison with example 9 in which a compound having a fluorine atom was not copolymerized.

From examples 19 and 20, it is clear that when the λ/4 layer was coated with the polymer of the present invention, and the liquid crystal layer 1 containing the polymer of the present invention was coated thereon, the evaluation was a among all properties. It was found that the polymer of the present invention is also effective for improving dishing and the like when the polymer is applied by lamination coating.

Examples 1 to 8, 11, 19 and 20 in which the amount of addition of the polymer of the present invention was 0.03 to 0.1 part by mass were excellent in all evaluation articles in the lower layer and the upper layer and were a or more.

Examples 1,2 and 4 in which the amount of the polymer of the present invention added was 0.04 to 0.05 part by mass were superior in orientation to examples 14 to 16 in which the same polymer was added in an amount of 0.4 to 0.7 part by mass.

Example 7 in which the amount of the polymer of the present invention added was 0.04 parts by mass was more excellent in evaluation of dishing than example 18 in which the amount of the polymer added was 0.01 parts by mass.

The compound having fluorine atoms in example 10 has a lower fluorine atom content than in examples 1 to 3, and therefore the surface tension is improved and the performance is reduced.

On the other hand, comparative example 1 having no hydroxyl group, comparative example 2 containing a polymer having not less than 2 radical polymerizable double bonds, and comparative example 3 containing a conventional fluorine-based surfactant were all evaluated as D in the lower layer, and were inferior. Comparative example 4, which did not contain the polymer of the present invention, was inferior in evaluation of D.

Claims

1. A polymer obtained by polymerizing a monomer having 2 or more radically polymerizable double bonds and 1 or more hydroxyl groups with a compound having a fluorine atom in an amount of 0.5 to 30 mol based on 1 mol of the monomer,

the monomer is represented by the following general formula X,

in the general formula X, Z^X1、Z^X2Each independently represents a group having a radically polymerizable double bond, L^X1、L^X4Each independently represents a single bond or an alkylene group having a hydroxyl group, L^X2、L^X3Each independently represents a single bond, or an alkylene group having a hydroxyl group and selected from the group consisting of-O-, - (C ═ O) O-, -O (C ═ O) -, and a 2-valent chain groupAnd a 2-valent linking group composed of at least one group of a 2-valent aliphatic cyclic group, M represents a single bond or a 2-to 4-valent linking group, n represents an integer of 1 to 3,

the radical polymerizable double bond-containing group is selected from the group represented by the following formulas Z1 to Z6, wherein R is^mRepresents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

the number of carbon atoms of the alkylene group in the alkylene group having a hydroxyl group is 1 to 12,

the chain group having a valence of 2 is an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, or an alkynylene group having 2 to 12 carbon atoms,

the aliphatic ring contained in the 2-valent aliphatic cyclic group is a cyclohexane ring, a cyclopentane ring or a norbornene ring,

the 2-to 4-valent linking group is a 2-to 4-valent chain group, a group having an aliphatic cyclic group, or a group having an aromatic ring, the 2-to 4-valent chain group is a saturated hydrocarbon group having 2 to 4 connecting bonds and having 1 to 40 carbon atoms, the aliphatic ring in the group having an aliphatic cyclic group is a cyclohexane ring, a cyclopentane ring, or a norbornene ring, the group having an aromatic ring is a phenyl group or a naphthyl group,

the compound having a fluorine atom is represented by the following general formula a,

2. The polymer of claim 1, wherein,

the monomer is represented by the following general formula X1,

in the formula X1, R¹、R²、R³Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, L¹¹、L¹²、L¹³Each independently represents a 2-valent linking group having a single bond or at least one group selected from the group consisting of-O-, - (C ═ O) O-, -O (C ═ O) -, a 2-valent chain group, an alkylene group having a hydroxyl group, and a 2-valent aliphatic cyclic group, and M¹Represents a single bond or a 2-or 3-valent linking group, n1 represents an integer of 0 to 2,

the 2-or 3-valent linking group is a 2-or 3-valent chain group, a group having an aliphatic cyclic group, or a group having an aromatic ring, the 2-or 3-valent chain group is a saturated hydrocarbon group having 2 to 3 connecting bonds and having 1 to 40 carbon atoms, the aliphatic ring in the group having an aliphatic cyclic group is a cyclohexane ring, a cyclopentane ring, or a norbornene ring, and the group having an aromatic ring is a phenyl group or a naphthyl group.

3. The polymer according to claim 1, wherein the monomer is represented by the following general formula X2,

R¹、R²is a hydrogen atom or a methyl group,

L¹¹、L¹²are respectively-O-CH₂-**、*-OCH(CH₃)-**、*-O-C₂H₄-**、*-O-C₃H₆-₂CH(OH)CH₂Bonded to the alkyl side having a hydroxyl group in the formula X2¹，

M¹Is a single bond, -C₆H₁₀-、-O(C＝O)C₆H₄(C＝O)O-、-O(C＝O)C₆H₁₀(C ═ O) O-, or-O-C₆H₄-C(CH₃)(CH₃)-C₆H₄-O-。

4. The polymer of claim 1, wherein,

the weight average molecular weight of the polymer is 1,000-300,000 in terms of polystyrene conversion based on gel permeation chromatography.

5. The polymer of claim 4, wherein,

the weight average molecular weight of the polymer is 1,000-10,000 in terms of polystyrene conversion based on gel permeation chromatography.

6. The polymer of claim 1 having a hyperbranched structure.

7. A composition comprising the polymer of any one of claims 1 to 6.

8. The composition of claim 7, further comprising a liquid crystal compound.

9. The composition of claim 8, wherein,

the liquid crystal compound is a polymerizable liquid crystal compound.

10. The composition of claim 9, wherein,

the polymerizable liquid crystal compound is at least one of a polymerizable rod-like liquid crystal compound and a polymerizable discotic liquid crystal compound.

11. An optical film comprising a cholesteric liquid crystal layer containing the polymer according to any one of claims 1 to 6 on a support.

12. The optical film according to claim 11, which has a structure in which a plurality of the cholesteric liquid crystal layers are stacked.

13. The optical film according to claim 12,

one of the cholesteric liquid crystal layers is a cholesteric liquid crystal layer including a rod-shaped liquid crystal compound, and the other is a cholesteric liquid crystal layer including a discotic liquid crystal compound.

14. The optical film according to claim 13,

the cholesteric liquid crystal layer including a rod-shaped liquid crystal compound and the cholesteric liquid crystal layer including a discotic liquid crystal compound are in contact with each other.

15. A liquid crystal display device comprising at least a backlight unit and a liquid crystal unit, each of which comprises the optical film according to any one of claims 11 to 14.